CN103108980A - Method for treating a surface of a device for dispensing a fluid product - Google Patents

Method for treating a surface of a device for dispensing a fluid product Download PDF

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Publication number
CN103108980A
CN103108980A CN2011800376936A CN201180037693A CN103108980A CN 103108980 A CN103108980 A CN 103108980A CN 2011800376936 A CN2011800376936 A CN 2011800376936A CN 201180037693 A CN201180037693 A CN 201180037693A CN 103108980 A CN103108980 A CN 103108980A
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pending
polymer elements
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Z·萨拉克
D·比萨多
F·盖尔纳莱克
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Aptar France SAS
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Valois SAS
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Priority claimed from FR1055371A external-priority patent/FR2962139B1/en
Priority claimed from FR1002868A external-priority patent/FR2962448B1/en
Application filed by Valois SAS filed Critical Valois SAS
Publication of CN103108980A publication Critical patent/CN103108980A/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48—Ion implantation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/0055—Other surface treatment of glass not in the form of fibres or filaments by irradiation by ion implantation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/14—Plasma, i.e. ionised gases
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M15/00—Inhalators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2205/00—General characteristics of the apparatus
    • A61M2205/02—General characteristics of the apparatus characterised by a particular materials
    • A61M2205/0233—Conductive materials, e.g. antistatic coatings for spark prevention
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Abstract

The invention relates to a method for treating a surface of a device for dispensing a fluid product, said method including a step of modifying, by ion implantation using beams of ions having multiple charge states and multiple energy states, at least one surface to be treated of at least one portion of said device, which is in contact with said fluid product, said modified surface to be treated having anti-adhesive properties for said fluid product, said ions having multiple charge states being selected from among those of helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (AR), krypton (Kr), and xenon (Xe), and the ion implantation being carried out at a depth of 0 to 3 [mu]m.

Description

The surface treatment method of the partitioning device of fluid product
Technical field
The present invention relates to the surface treatment method of the partitioning device of fluid product.
Background technology
The partitioning device of fluid product is known.They comprise storage tank, distribution member for example pump or valve usually, and the distributor head that is equipped with dispensing orifice.Perhaps, in a kind of modification, the fluid product partitioning device can be the sucker that comprises a plurality of storage tanks, and each storage tank contains individually dosed powder or liquid, and the device of opening and discharge described dosage for the driving process in succession.Thereby this equipment is included in a plurality of parts that come in contact with fluid in the driving process.Therefore, exist fluid to adhere to before being assigned to the user or be deposited in the risk on one or more parts of equipment.This causes the dosage distributed to compare reduction with theoretical dose, and this can form serious problems, for example is used for the treatment of for example asthma attack that shows effect.Sticking problem can occur in storage tank especially, but also can occur in piston and pump chamber, or valve and valve pocket.This is equally applicable to thruster or dispenser head.
For Diskus, when delivering active ingredients, on all walls in powder often sticks to its path, from the storage tank that contains it to the mouthpiece contacted with the patient.The using for the first time in delivery process of sucker that stick to like this is bad especially.This adhesion of activeconstituents affects the homogeneity for activeconstituents and the milk-sugar mixture of this preparation potentially.In causing the possible reason adhered to, can mention especially: the impact of the static electric charge on the wall contacted with powder along dispense path; The impact of condition of surface (roughness, microdefect etc.); The type (particularly plastics, metal) of the material used; The activeconstituents per-cent of the particle diameter of the type of preparation, particularly powder or every dosage; And the discharge condition of dosage (flow rate, speed etc.).
The equal existent defect of all existing surface treatment methods.Therefore, some mode only is applicable to flat surface.The selection of other method restriction base material, for example be restricted to gold.The plasma induced polymerization of molecule is complicated and expensive, and the coating obtained is difficult to control and exist problem of aging.Similarly, be also complicated and expensive with the polymerization of uv-radiation inducing molecule, and only photosensitive molecular worked.This also is applicable to atom transfer radical polymerization (ATRP), and it is also expensive and complicated.Finally, the electronics grafting method is complicated, and requires the conductive carrier surface.
Summary of the invention
The objective of the invention is to propose the surface treatment method that does not there is above-mentioned shortcoming.
Particularly, the present invention aims to provide surperficial treatment process, and the method is effective, lasting, pollution-free and implements simple.
Particularly, the invention provides by the method for the ion processing polymer elements of multi-charge and multipotency, described ion belongs to the group consisted of helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), this polymer elements forms the part of fluid dispensing apparatus, especially for medicine.
Most of commercial polymer non-conducting electric current.Their surface resistivity is 10 15to 10 17between Ω/.
Yet, due to many reasons, may need electroconductibility, these reasons comprise:
-anti-electrostatic effect: the surface resistivity reduction that continues a few weeks or months can be enough.
The dissipation of-static charge: this is by dissipative material and conductor realization, and they prevent that electric discharge the charge dissipation that high-speed mobile is caused from falling.
-electromagnetic shielding: the material that need to there is very low volume specific resistance (<1ohm.cm).Must conformance with standard electromagnetic radiation from the product of manufacturing with restriction.
Can obtain electroconductibility by number of ways:
-volatile additive, for example aliphatic amide ester or quaternary amine.These materials of bringing in polymeric matrix migrate to surface and react with airborne moisture.They are reduced to surface resistivity by surface, forming moisture film approximately 10 14Ω/.
The filler of-permanent reduction surface resistivity and volume specific resistance.Particularly, they are carbon black, carbon fiber, graphite, Stainless Steel Fibre, aluminium bits, carbon nanotube.When only needing antistatic surface or static charge dissipation electrical property, these fillers excessively improve the polymers manufacturing cost.
The polymkeric substance of-conduction own.They are costliness but also to the working conditions sensitivity not only.Heat and moisture make their electrical property deteriorated rapidly.
Adhering to is the remarkable phenomenon of polymkeric substance, and it shows as for example biologically active prod adhesion from the teeth outwards.This adheres to the contribution that comes from the Van der Waals force that the electrostatic force that very high surface resistivity induces and the polarity that is positioned at the molecule of polymer surfaces produce.
Except adhesion problems, polymer elements often need to be in either large or small rodent chemical mediator, in ambient moisture, in ambient oxygen etc. be worked under condition, and this can cause by oxidation the raising of their electrical insulating property.
For some polymkeric substance, the chemical reagent of protection UV, oxidation is filled.The discharge laterally of these chemical reagent has the effect of accelerating surface oxidation, and this has strengthened again the insulativity of polymkeric substance.
The present invention is intended to reduce above-mentioned shortcoming, particularly significantly reduces the surface resistivity of polymkeric substance solid parts, keeps its body elastic performance simultaneously and prevents from using the chemical reagent of insalubrity.
Thereby the present invention especially provides at least one the surperficial method with helium ion processing polymkeric substance solid parts, it is characterized in that multipotency ion X +and X 2+implant, wherein ratio R X is less than or equal to 100, for example is less than 20, wherein RX=X simultaneously +/ X 2+, wherein X belongs to the list of helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe) formation, X +and X 2+with atomic percent, mean.
As example, the contriver can prove, and wherein only implants He +or He 2+the known treatment of ion is compared, He +and He 2+there is the antistatic surface performance that can improve very significantly polymkeric substance in the time of ion.They can prove, for example, for being less than or equal to 100, being less than or equal to 20 RHe, obtain significantly and improve.
It should be pointed out that the present invention can reduce the surface resistivity of polymkeric substance solid parts and/or eliminate adhering to of dust, even for example OH, COOH reduce Surface Polarization to the chemical group by removing high degree of polarization.These functional groups can induce Van der Waals force, and it has the effect that the chemical molecular in environment is bonded to polymer surfaces.
The present invention also can improve the chemical stability of polymkeric substance, for example, by forming permeability barrier.This ambient oxygen propagation in polymkeric substance of can slowing down, and/or delay chemical protector contained in polymkeric substance to external diffusion, and/or suppress contained outside the separating out of toxic agent in polymkeric substance.
Advantageously, the present invention can and replace them for the interpolation of omitting chemical reagent or filler with physical method, described physical method be applicable to the polymkeric substance of any type and aspect the consumption of material and energy cost lower.
Within the scope of the present invention, term " solid " refers to machinery or the physical deformation by material block, for example by extruding, molding or be applicable to any other technology of polymer blocks distortion, the polymer elements of producing.
As example, in polymkeric substance, can mention the following material of advantageously processing according to the present invention:
-polycarbonate (PC)
-polyethylene (PE)
-polyethylene terephthalate (PET)
-polymethacrylate (PMMA)
-polypropylene (PP)
-polyamide (PA).
Due to method of the present invention, can process the much bigger degree of depth, this has represented high chemical stability, shows as keeping very for a long time of surperficial electric property (antistatic, static charge dissipating).
Proved the treatment time with regard to industrial requirements and Yan Buchang.
In addition, the method is low-yield, cheaply, and can in the situation that without any environmental influence for industrial circle.
The processing of polymer elements by implanting multipotency simultaneously, multiplycharged ion carries out.These ions are particularly used the single charge ion and the multiplycharged ion that form in the plasma chamber of single extraction voltage subtraction electron cyclotron resonance ion source (RCE source) to obtain.The every kind of ion produced by described source has energy proportional to its state of charge.Show that thus the ion that has the highest state of charge thereby have a highest energy implants in polymer elements with the maximum degree of depth.
With the implantation in RCE source, be quick and cheap, because it does not need the ionogenic high voltage that extracts.In fact, in order to improve the implantation energy of ion, preferably improve economically its state of charge rather than improve its extraction voltage.
It should be pointed out that conventional source, for example, especially by the source of plasma immersion or filament implanting device implanting ions, can not obtain and be suitable for implanting multipotency ion X simultaneously +and X 2+ionic fluid, wherein ratio R X is less than or equal to 100.On the contrary, use such source, it is more than or equal to 1000 usually.
The contriver can prove, and the method can be for carrying out surface treatment in the situation that do not change the body elastic performance of polymer elements to polymer elements.
According to a kind of embodiment of the present invention, this source is the electron cyclotron resonance source, and it is created at the temperature that is less than 50 ℃ implants the multipotency ion in parts, and the implantation of the ion of implantation bundle is carried out with the voltage-controlled degree of depth of the extraction that is subject to source simultaneously.
Do not wish to be limited to special scientific theory, can think in the method for the invention, when ion passes through, they have excited the electronics of polymkeric substance, cause the covalent linkage fracture, this covalent linkage recombinates to obtain by being called crosslinked mechanism the highdensity covalent chemical bond mainly consisted of carbon atom immediately.Lighter element for example hydrogen and oxygen is discharged from polymkeric substance in degasification process.This densification to rich carbon covalent linkage has following effect: improve surface conductivity, and reduce the surface polarity group of even removing as the Van der Waals force source, this Van der Waals force is the source of adhering to.Ion is lighter, and cross-linking process is more effective.
Thereby helium is preferred favourable projectile body, because:
-it with the speed of the electronics of covalent linkage, compare very fast, thereby it excite aspect these electronics very effective, described electronics thereby the not free track that changes them,
-it penetrates the micron-sized large degree of depth,
-it is not dangerous,
-as rare gas, it does not affect the chemical constitution of polymkeric substance.
Can consider easy-to-use, for example, without any the ion of other type of health risk, nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe).
According to the different preferred embodiment of the inventive method, they can be bonded to each other.A kind of preferred embodiment is for example will what follows combine:
-ratio R He is more than or equal to 1, wherein RHe=He +/ He 2+, He wherein +and He 2+with atomic percent, mean;
-implantable multipotency IONS OF H e +and He 2+the extraction voltage in source between 10 to 400kV, for example be more than or equal to 20kV and/or be less than or equal to 100kV;
-multipotency IONS OF H e +and He 2+dosage 5 * 10 14to 10 18ion/cm 2between, for example be more than or equal to 10 15ion/cm 2and/or be less than or equal to 5 * 10 17ion/cm 2, even be more than or equal to 5 * 10 15ion/cm 2and/or be less than or equal to 10 17ion/cm 2;
-in preliminary step, determine that the evolution of characteristic performance on solid polymer elements surface is along with multipotency IONS OF H e +and He 2+the variation of dosage, for example, as the surface resistivity of the polymkeric substance of the polymer materials of the representative of pending parts, to determine the scope of ion dose, in this scope, the variation of selected characteristic performance is favourable, and in three ion dose zones in succession that form described ion dose scope, develop in a different manner, evolution in first area is substantial linear, and be less than one month during be reversible, evolution in second area is substantial linear, and be stable during over one month, last evolution in the 3rd zone is constant, and be stable during over one month, and wherein select the multipotency IONS OF H e in the 3rd ion dose zone +and He 2+dosage to process solid polymer elements, the reversible evolution (first area) of term refers to resistivity decreased and then is increased to its original value.This phenomenon is the weather resistance after implantation due to free radical, and the oxygen in it and ambient air is compound, thereby causes the raising of surface resistivity.
-adjust the movement on surface of pending polymer elements and the parameter in source, make the surface treatment speed on pending polymer elements surface at 0.5cm 2/ s to 1000cm 2between/s, for example be more than or equal to 1cm 2/ s and/or be less than or equal to 100cm 2/ s;
-adjust the movement on surface of pending polymer elements and the parameter in source, make the helium dosage of implantation 5 * 10 14to 10 18ion/cm 2between, for example be more than or equal to 5 * 10 15ion/cm 2and/or be less than or equal to 10 17ion/cm 2;
-adjust the movement on surface of pending polymer elements and the parameter in source, make helium at the lip-deep depth of penetration of treated polymer elements between 0.05 to 3 μ m, for example be more than or equal to 0.1 μ m and/or be less than or equal to 2 μ m;
-adjust the movement on surface of pending polymer elements and the parameter in source, make the surface temperature of polymer elements in treating processes be less than or equal to 100 ℃, for example be less than or equal to 50 ℃;
-polymer elements is for example irregular bar, and described parts are advanced with the speed of for example 5m/min to 100m/min in treatment facility; For example, the irregular bar of this polymer elements for vertically advancing;
-by a plurality of multipotency He that produced by a plurality of ion sources +and He 2+ionic fluid, by helium implantation from the surface of pending parts; For example, ion source is along the travel direction setting of pending parts; Preferably, by these sources, the spaced apart so that distance between two ionic fluids is enough to allow parts cooling between implanted ions in succession at each; The diameter of the ionic fluid that described source produces is suitable for the width of pending track.For example, by the diameter by bundle, be down to 5mm, can settle very effective differential vacuum system between source and treatment chamber, these can be 10 -2process polymkeric substance under mbar, and the vacuum of source extraction system is 10 -6mbar;
The polymkeric substance of-parts is selected from polycarbonate, polyethylene, polyethylene terephthalate, polymeric amide, polymethacrylate, polypropylene.This is enumerated and is not exhaustive.Also can consider the polymkeric substance of other conventional crosslinkable type.
The invention still further relates to parts, the thickness that wherein helium is implanted is more than or equal to 50nm, for example be more than or equal to 200nm, and its surface resistivity ρ is less than or equal to 10 14Ω/, for example be less than or equal to 10 9Ω/, even be less than or equal to 10 5Ω/.For the measurement of Surface factor, referring to IEC standard 60093.
Thereby, the invention provides the surface treatment method of fluid product partitioning device, described method comprises the step that the ionic fluid with multi-charge and multipotency carries out modification by least one pending surface of at least a portion of the implanted ions pair described equipment contacted with described fluid product, the described pending list mask of modification has the anti-adhesive properties for described fluid product, described multiplycharged ion is selected from helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and implanted ions proceeds to the degree of depth of 0 to 3 μ m.
Favourable embodiment is recorded in dependent claims.
Particularly, described method comprises at least one the surperficial method with ion processing polymkeric substance solid parts, and described method comprises with multipotency ion X +and X 2+the ion bombardment of the ionic fluid formed, wherein X is the atomic symbol that is selected from the ion of helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), wherein RX=X +/ X 2+be less than or equal to 100, for example be less than 20, X +and X 2+mean with atomic percent, wherein in preliminary step, determine the translational speed of bundle, determine the minimum translational speed of the bundle that does not cause the polymkeric substance thermal destruction in this step, described thermal destruction improves 10 by pressure -5mbar shows.
The accompanying drawing explanation
These and further feature of the present invention and advantage will become clearer in the following detailed description, and these explanations are especially undertaken by the accompanying drawing with reference to providing as limiting examples, wherein:
Fig. 1 illustrates the example that helium according to the present invention is implanted in the distribution in polycarbonate;
Fig. 2 illustrates the yardstick of the different standards of the antistatic property of describing material;
Fig. 3 illustrates for multiple helium dosage, and the surface resistivity of the polycarbonate sample surfaces of processing according to the present invention over time; Surface resistivity is used electrode measurements according to IEC standard 60093, described electrode by the ring that is D by internal diameter around diameter be d dish forms, wherein D is greater than d;
Fig. 4 illustrates for three kinds of IONS OF H e, N and Ar, and according to multiple dosage, the surface resistivity of the polycarbonate sample surfaces of processing according to the present invention over time; Surface resistivity is measured according to IEC standard 60093; And
Fig. 5 illustrates for multiple nitrogen dosage but, according to two kinds of bundle translational speeds, the surface resistivity of the polycarbonate sample surfaces of processing according to the present invention over time.Surface resistivity is measured according to IEC standard 60093.
Embodiment
Particularly, the present invention considers to use and the similar method described in document WO2005/085491, it relates to ion implantation method, more specifically to using multi-charge multipotency ionic fluid, in order in the about degree of depth of 1 micron, the surface of metallic substance is carried out structurally-modifiedly, think that they provide specific physicals.This method for implantation has been used in particular for processing the parts of being produced by aluminium alloy, and these parts are as the mould of the scale operation of plastic components.
Surprisingly, proved that such method is suitable for the surface that modification will contact with the medicinal fluid product in partitioning device, to prevent that the fluid product is in described lip-deep adhesion.This application of ion implantation method never was considered before this.Thereby the description of document WO2005/085491 is all included in this specification sheets by reference.
Pending surface can comprise synthetic materials, for example polyethylene (PE) and/or polypropylene (PP) and/or polyvinyl chloride (PVC) and/or polytetrafluoroethylene (PTFE).They can be also metal, glass or elastomerics material.
Particularly, for Diskus, the dosage of powder predose in independent storage tank wherein, the inventive method suppresses the effect of static electric charge, and the frictional behaviour on the surface that change contacts with powder, thereby alleviate powder by the risk of the adhesion at place, this is specially adapted to first dosage of discharging.
Briefly, the method is to use one or more ion sources, and for example the electron cyclotron resonance source, be called the RCE source.Initial multipotency ionic fluid can be sent in this RCE source, and for example all electric charge of about 10mA(is together under can the extraction voltage in 20kV to 200kV scope) total current.The RCE source is the emitting ions bundle on the direction of setting device, and this device focuses on and be adjusted to the implantation particle beam by the initial bundle of RCE source emission, and this particle beam impacts pending parts.According to application and pending material, ion can be selected from helium, boron, carbon, nitrogen, oxygen, neon, argon, krypton, xenon.Similarly, the maximum temperature of pending parts is along with its kind changes.Typical implantation depth, in 0 μ m to 3 μ m scope, and not only depends on and also depends on performance to be improved in pending surface.
The ionogenic singularity of RCE mainly is that it sends single electric charge and multiplycharged ion, this means that the multipotency ion can be used identical extraction voltage to implant simultaneously.Thereby can obtain the implantation profile distributed suitably on treated whole thickness simultaneously.This improves the surface-treated quality.
Advantageously, the method is carried out in the chamber emptying by vacuum pump.This vacuum is used for preventing the interception of residual gas to ionic fluid, and prevents the pollution of gas identical described in implantation process to parts surface.
Advantageously, and particularly described in document WO2005/085491, from the RCE source, to pending parts, above-mentioned setting device comprises following elements:
-mass spectrograph, it can be according to electric charge and the quality filter ions thereof of ion.Yet, if inject scrubbed gas, pure nitrogen (N2) for example, such spectrometer is optional.Thereby all single electric charge can the source of reclaiming produced and multiplycharged ion are to obtain the multipotency ionic fluid;
-one or more lens, so that the ionic fluid with predetermined shape to be provided, for example have the cylindrical of predetermined radii;
-profiler (profileur), with in the process in the first implantation in vertical cutting plane the intensity of analysed beam;
-intensity transformation device, with in the situation that do not block the intensity that ionic fluid is measured ionic fluid continuously.This instrument mainly detects any interruption in ionic fluid, and makes in can record process the variation of the intensity of restrainting;
-shutter, it can be for example Faraday's cage, for example, at a time to interrupt the track of ion, in there is no the moving process of processing element.
In a kind of favourable embodiment, pending parts are removable with respect to the RCE source.These parts can for example be installed on movable carrier, and this carrier is used under the control of numerically-controlled machine.The movement of pending parts is calculated according to following factor: the radius of bundle, the outside in pending zone and in-profile, the constant or variable translational speed as bundle with respect to the function of surperficial angle, and the road number carried out.
A kind of possible embodiment of this treatment process is as follows.Pending parts are fixed on suitable carrier in chamber, then chamber are closed, and use vacuum pump that strong vacuum is set.Once reach vacuum condition, start and adjust ionic fluid.When adjusted described bundle, shutter is risen and start numerically-controlled machine, thereby this machine is controlled position and the translational speed of pending parts in the bundle front in one or more passages.When reaching required road number of times, shutter is fallen to cut off bundle, the production of bundle is stopped, by chamber is opened and interrupted vacuum to ambient air, cut off where necessary cooling loop, and treated parts are removed from chamber.
For the relevant temperature of passing through of the set point that is reduced in pending parts and ionic fluid, or the radius that can improve bundle is (to reduce every cm 2power), or can improve translational speed.To such an extent as to can not discharge the heat relevant to processing by irradiating if parts are too little, so or can reduce the power (improving treatment cycle) of bundle, or open cooling loop.
Especially for elastomerics, advantageously implant multipotency helium IONS OF H e simultaneously +and He 2+.This is recorded in document PCT/FR2010/050379 especially, and it is included in herein by reference, and the document relates more particularly to the windscreen wiper of vehicle.Advantageously, ratio R He is less than or equal to 100, for example is less than 20, and is preferably more than 1, wherein RHe=He +/ He 2+, He wherein +and He 2+with atomic percent, mean.He +and He 2+ion advantageously produces by a RCE source simultaneously.Can realize multipotency He +and He 2+the extraction voltage in the source of the implantation of ion can, in 10kV to 400kV scope, for example be more than or equal to 20kV and/or be less than or equal to 100kV.Advantageously, multipotency He +and He 2+the dosage of ion is 10 14to 10 18ion/cm 2in scope, for example be more than or equal to 10 15ion/cm 2and/or be less than or equal to 10 17ion/cm 2, or be more than or equal to 10 15ion/cm 2and/or be less than or equal to 10 16ion/cm 2.Implantation depth is advantageously in 0.05 μ m to 3 μ m scope, for example, in 0.1 μ m to 2 μ m scope.The temperature of surface of elastomer in treating processes advantageously is less than 100 ℃, preferably is less than 50 ℃.
In a kind of favourable embodiment, carry out different implanted ions on identical pending surface, on this pending surface, to produce multiple performance.Thereby, surface of elastomer, especially for the distributing fluids seal washer of the partitioning device of medicine for example, metal or glass surface, perhaps synthetic surface is for example made by polyethylene or polypropylene, can with fluid interaction, for example, by extractable matter is leached in described fluid, and this can have deleterious effect to described fluid.Advantageously, the present invention can be used for the pending surface of modification, with prevent or limit fluid and pending surface between interaction.These additional surface treatments can apply in implanted ions process in succession.It should be noted that these implanted ions in succession can carry out with any order.In a kind of modification, also can different performances be put on to identical pending surface in same implanted ions step process.
The inventive method is free of contamination, particularly because it does not need chemical.It is implemented with dry method, so it avoids the relatively long drying cycle relevant to liquid treating method.Need to there be sterile atmosphere in it in the vacuum chamber outside; Thereby it can be implemented anywhere.A special advantage of the method is that it can be incorporated in the assigned line of fluid product partitioning device and operate continuously in this line.The integration of this treatment process in means of production simplified and accelerated manufacture and assembling process as a whole, thereby its cost is had to favourable influence.
The present invention is applicable to multiple doses equipment for example pump or valve device, and this pump or valve device are installed on storage tank and drive with administered in succession.It also can be applied to comprise the multiple doses equipment of a plurality of independent storage tanks, and each storage tank contains a fluid dosage, for example powder inhalator of predose.It also can be applied to single or dose double equipment, wherein in each driving lower piston directly moves to storage tank.Particularly, the present invention can be applied to nose or mouthful spraying equipment, is applied to partitioning device and the injector type needle-like equipment of ophthalmic applications.
Fig. 1 to 5 illustrates favourable embodiment of the present invention.
Fig. 1 illustrates according to the present invention in polycarbonate helium and distributes along with the implantation of the degree of depth.Curve 101 is corresponding to He +distribution, curve 102 is corresponding to He 2+distribution.Can estimate, for 10
Figure BDA00002798872300101
mean ionization energy, for the energy of 100keV, He 2+cover the mean distance of about 800nm.For 4
Figure BDA00002798872300102
mean ionization energy, for the energy of 50keV, He +cover the mean distance of about 500nm.The ionization energy of ion is relevant to its crosslinked ability.As (He +/ He 2+) be less than or equal at 100 o'clock, can estimate that the maximum thickness of processing is i.e. 1 micron dimension of 1000nm.These estimate consistent with the observation by electron microscope, and it has proved for the bundle and 5 * 10 extracted at 40kV 15ion/cm 2dosage and (He +/ He 2+)=10, observe the cross-linked layer of about 750nm to 850nm.
Fig. 2 illustrates the resistivity value of the antistatic property of describing material, according to standard DOD HDBK263.For being greater than 10 14the surface resistivity values of Ω/ (regional I), polymkeric substance has insulating property, for 10 14Ω/ to 10 9surface resistivity values (regional A) in Ω/ scope, have antistatic property.For 10 5Ω/ to 10 9surface resistivity values (regional D) in Ω/ scope, show the static charge dissipative performance, for being less than 10 5the value of Ω/ (regional C), show conductivity.
Fig. 3 illustrates for 10 15(curve 1), 2.5 * 10 15(curve 2), 5 * 10 15ion/cm 2(curve 3), 2.5 * 10 16ion/cm 2the different helium dosage of (curve 4), at He +/ He 2+under=10 conditions, the surface resistivity of polycarbonate is along with the experiment of time changes; Extracting voltage is about 40kV.Resistivity measurement is carried out according to IEC standard 60093.The resistivity measurement technology of using can not be measured and be greater than 10 15the resistivity of Ω/, it is corresponding to regional N; It is 10 15Ω/ is saturated.X-coordinate is corresponding to processing sample and measure the time between its surface resistivity.Ordinate zou, corresponding to the measurement of surface resistivity, means with Ω/.For being less than or equal to 10 15ion/cm 2dosage can observe a first area, wherein surface resistivity reduces approximately 3 orders of magnitude (from 1.5 * 10 being less than in one month 16Ω/ to 5 * 10 12Ω/), then recover its approximately 1.5 * 10 16the original value of Ω/ (curve 1).In this zone, antistatic property is of short duration, and the free radical and the oxygen in ambient air that still exist are compound.In second area, can see that resistivity is along with dosage reduces: 2.5 * 10 15ion/cm 2, 5 * 10 15ion/cm 2, 2.5 * 10 16ion/cm 2scope, surface resistivity is from 10 11Ω/ is down to 5 * 10 9Ω/, be estimated as approximately 1.5 * 10 until it reaches 8the saturated platform of Ω/.Antistatic property (curve 2 and 3) is strengthened and becomes can dissipation of static charge (curve 4).For these dosage, it is constant that resistivity keeps within surpassing 140 days.For 2.5 * 10 16ion/cm 2dosage, reach the 3rd zone, wherein the variation of resistivity is being estimated as approximately 10 according to dosage 8the value of Ω/ is saturated, and within surpassing 140 days, keeps constant.
Fig. 4 illustrates for three kinds of IONS OF H e(curves 1), N(curve 2) and Ar(curve 3), for 10 15ion/cm 2, 5 * 10 15ion/cm 2with 2.5 * 10 16ion/cm 2various dose, at (He +/ He 2+)=10, (N +/ N 2+)=2 and (Ar +/ Ar 2+under the condition of)=1.8, the surface resistivity of polycarbonate (PC) is along with the experiment of time changes.Beam diameter is 15mm, and electric current is 0.225mA; Extracting voltage is about 35kV.X-coordinate means the ion dose of per unit surface-area, with 10 15ion/cm 2mean.Ordinate zou presentation surface resistivity, mean with Ω/.Resistivity measurement is carried out according to IEC standard 60093.For identical dosage, the heaviest ion is the most effective aspect the reduction surface resistivity; The PC processed with nitrogen has than the surface resistivity of low at least 10 times of the PC processed with helium, and the PC processed with argon has than the surface resistivity of low at least 10 times of the PC processed with helium.The contriver advises using for example xenon of heavier ion, further to reduce the surface resistivity of polycarbonate.
Fig. 5 illustrate for the ion of same type but under two kinds of different bundle translational speeds (translational speed of 80mm/s (curve 1), the translational speed of 40mm/s (curve 2)), for 10 15ion/cm 2, 5 * 10 15ion/cm 2with 2.5 * 10 16ion/cm 2various dose, at (N +/ N 2+under the condition of)=2, the surface resistivity of polycarbonate is along with the experiment of time changes.Beam diameter is 15mm, and electric current is 0.150mA; Extracting voltage is about 35kV.X-coordinate means the ion dose of per unit surface-area, with 10 15ion/cm 2mean.Ordinate zou means area resistivity, with Ω/, means.Conductivity measurement is carried out according to IEC standard 60093.Can find out Speed Reduction to two/mono-to be there is to the effect that the surface resistivity of PC is reduced to 1/10th from these curves.Do not wish to be limited by any specific scientific theory, can think the speed of restrainting by reduction, the surface resistivity of PC improves.This temperature significantly improves each other compound of free radical, promotes to form the conducting film of the densification of decolorizing carbon simultaneously.Heating also has the effect that residual gas that fracture/mechanism of crosslinking that ion bombardment is caused produces is discharged.The contriver draws from this experiment, any polymkeric substance of processing for the bundle with thering is known diameter and power, have tuftlet translational speed, this speed causes the maximum of polymer surfaces resistivity to reduce, and under the effect of produced heat, does not make the risk of polymer degradation simultaneously.The thermal destruction of polymkeric substance is by significantly degassed and show for the raising of the pressure of the extraction system in RCE source subsequently.The raising of this pressure proves that himself is in electrical breakdown.Extraction system plays from the plasma body in RCE source and extracts ion to form the effect of bundle.It consists of two electrodes, first ground connection, and second is being less than 5 * 10 -6mbar, preferably be less than 2 * 10 -6the vacuum condition of mbar is issued to the high pressure of tens kV.Surpass these pressure and produce electric arc.When this occurs in polymkeric substance generation thermal destruction.Therefore should detect these pressure risings very early, by reduction gradually, restraint translational speed and monitor that the pressure change in extraction system carries out.
In order to determine this bundle translational speed, the contriver recommends a kind of test procedure, and it is to reduce gradually the speed of bundle, keeps further feature simultaneously:
-Shu Tezheng: diameter, power is intensity, and extracts voltage;
-dynamic characteristic: mobile range, speed of advance.
When the pressure rise of the gage measuring by being arranged in extraction system and treatment chamber, at several seconds, the even shorter time jumped 10 -5during mbar, polymkeric substance issues the heat-dissipating degraded in hot effect.Test must stop immediately, the translational speed in the test before only being retained in.Jumped 10 within several seconds even shorter time -5mbar forms the sign of polymkeric substance thermal destruction.
Several characterizing methods can be emphasized advantage of the present invention.
In example below, with passing through the produced simultaneously multipotency He in RCE source +and He 2+ion carries out by helium IONS OF H e +and He 2+implantation to the processing at least one surface of solid polymer elements.Processed polymkeric substance is particularly: polypropylene (PP) and polymethacrylate (PMMA).
Use is thrown away to and is processed the contrast test that relates to antistatic property that the small piece of paper on sample carries out and can show that it appears at and be greater than 5 * 10 15ion/cm 2situation under.For these dosage, when these sample upsets, the scraps of paper break away from and fall, and this is being less than 5 * 10 15ion/cm 2dosage under do not occur.
For polypropylene, for 10 15ion/cm 2with 5 * 10 15ion/cm 2dosage, can record 10 according to IEC standard 60093 14the surface resistivity of Ω/.For 2 * 10 16ion/cm 2dosage, can record 5 * 10 11the resistivity of Ω/, be equivalent to occur these antistatic properties.
In one embodiment, estimate from being greater than 5 * 10 15ion/cm 2the dosage antistatic surface performance that plays polymkeric substance significantly improve, for by 9mA He +ion and 1mA He 2+the helium bundle that ion forms, this has represented about 15cm 2the processing speed of/s.
According to requirement and the shape of pending parts, in the time of can be by the helium ion, implant and proceed to the different degree of depth.These degree of depth depend on the implantation energy of the ion of implanting bundle especially; For example, for polymkeric substance, they can be for 0.1 μ m to about 3 μ m.For the application that needs the non-sticky performance, the thickness that for example is less than 1 micron is just enough, for example further reduces handling duration.
In one embodiment, select to implant He +and He 2+the condition of ion, make polymer elements retain its body elastic performance by parts being remained under the treatment temp that is less than 50 ℃.Can obtain this result for the Shu Youqi with 4mm diameter, the total current that it provides 60 microamperes, have the extraction voltage of 40kV, with the speed of 40mm/s, on the mobile range of 100mm, moves.This bundle has 20W/cm 2power per unit area.When using identical extraction voltage and identical power per unit area, and more high-intensity bundle is while retaining the body elastic performance simultaneously, can draw a thumb rule, it is to improve mobile range, improve translational speed and improve the diameter of restrainting with a ratio, and described ratio is the square root divided by the business of 60 μ A corresponding to target current.As an example, for the electric currents of 6 milliamperes (100 being multiplied by 60 microamperes), this bundle should have the diameter of 40mm so that power per unit area is remained on to 20W/cm 2.Under these conditions, speed can be multiplied by the factor 10, and mobile range can be multiplied by the factor 10, obtains the speed of 40cm/s and the mobile range of 1m.Number of pass times also can be multiplied by the identical factor, in the end to obtain with ion/cm 2the identical treatment dosage meaned.When moving continuously, the number that is placed in the micro-accelerator on the transmission belt path for example also can be multiplied by the identical factor.
Also can find out, by treatment in accordance with the present invention, other surface property also obtains the improvement of highly significant; To have obtained the performance of using other technology not obtain.
The invention is not restricted to the embodiment of these types, and should explain in nonrestrictive mode, comprise the polymkeric substance of processing any type.
Similarly, method of the present invention is not limited to use the RCE source, even may think that other source will be not too favourable, method of the present invention can be used single ion source or use other multi-ion source to implement, as long as these sources of configuration are in order to can implant the multipotency ion that is selected from helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr) and xenon (Xe) simultaneously.
In the situation that do not depart from the scope of the invention of subsidiary claim definition, multiple change is also possible for those skilled in the art.

Claims (21)

1. the surface treatment method of fluid product partitioning device, it is characterized in that described method comprises the step that the ionic fluid with multi-charge and multipotency carries out modification by least one pending surface of at least a portion of the implanted ions pair described equipment contacted with described fluid product, the described pending list mask of modification has the anti-adhesive properties for described fluid product, described multiplycharged ion is selected from helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and implanted ions proceeds to the degree of depth of 0 to 3 μ m.
2. according to the process of claim 1 wherein that described multipotency ion implants with identical extraction voltage simultaneously.
3. according to the method for above claim any one, wherein said pending surface is synthetic materials, elastomerics, glass or metal material, and described synthetic materials especially comprises polyethylene (PE) and/or polypropylene (PP) and/or polyvinyl chloride (PVC) and/or polytetrafluoroethylene (PTFE).
4. according to the method for above claim any one, wherein the method also comprises and is imparted to less a kind of step of additional properties by implanted ions to described pending surface, for example reduces the interaction with fluid product.
5. according to the method for above claim any one, wherein said method is implemented continuously on the assigned line of the partitioning device of fluid product.
6. according to the method for above claim any one, wherein said method comprises at least one surface with ion processing polymkeric substance solid parts, and described method comprises with multipotency ion X +and X 2+the ion bombardment of the ionic fluid formed, wherein X is the atomic symbol that is selected from the ion of helium (He), nitrogen (N), oxygen (O), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), wherein RX=X +/ X 2+be less than or equal to 100, for example be less than 20, X +and X 2+mean with atomic percent, wherein in preliminary step, determine the translational speed of bundle, determine the minimum translational speed of the bundle that does not cause the polymkeric substance thermal destruction in this step, described thermal destruction improves 10 by pressure -5mbar shows.
7. according to the method for claim 6, its intermediate ion X +and X 2+by electron cyclotron resonance ion source (RCE), produce simultaneously.
8. according to the method for claim 6 or 7 any one, wherein ratio R X is more than or equal to 1.
9. according to the method for any one in claim 6 to 8, wherein can realize multipotency ion X +and X 2+the extraction voltage in the source of implanting, between 10 to 400kV, for example is more than or equal to 20kV and/or is less than or equal to 100kV.
10. according to the method for any one in claim 6 to 9, multipotency ion X wherein +and X 2+dosage 5 * 10 14to 10 18ion/cm 2between, for example be more than or equal to 10 15ion/cm 2and/or be less than or equal to 5 * 10 17ion/cm 2, even be more than or equal to 5 * 10 15ion/cm 2and/or be less than or equal to 10 17ion/cm 2.
11., according to the method for any one in claim 6 to 10, wherein in preliminary step, determine that the evolution of characteristic performance on solid polymer elements surface is along with multipotency ion X +and X 2+the variation of dosage, for example, as the surface resistivity ρ of the polymer materials of the representative of pending parts, to determine the scope of ion dose, in this scope, the variation of selected characteristic performance is favourable, and in three ion dose zones in succession that form described ion dose scope, change in a different manner, evolution in first area is substantial linear, and be less than one month during be reversible, evolution in second area is substantial linear, and be stable during over one month, the last evolution in the 3rd zone is constant, and be stable during over one month, and wherein select the multipotency ion X in the 3rd ion dose zone +and X 2+dosage to process solid polymer elements.
12. according to the method for any one in claim 6 to 11, wherein adjust the movement on surface of pending polymer elements and the parameter in source, make the surface treatment speed on pending polymer elements surface at 0.5cm 2/ s to 1000cm 2between/s, for example be more than or equal to 1cm 2/ s and/or be less than or equal to 100cm 2/ s.
13. according to the method for any one in claim 6 to 12, wherein adjust the movement on surface of pending polymer elements and the parameter in source, make the ion dose of implantation 5 * 10 14to 10 18ion/cm 2between, for example be more than or equal to 5 * 10 15ion/cm 2and/or be less than or equal to 10 17ion/cm 2.
14. the method according to any one in claim 6 to 13, wherein adjust the movement on surface of pending polymer elements and the parameter in source, make ion at the lip-deep depth of penetration of treated polymer elements between 0.05 to 3 μ m, for example be more than or equal to 0.1 μ m and/or be less than or equal to 2 μ m.
15., according to the method for any one in claim 6 to 14, wherein adjust the movement on surface of pending polymer elements and the parameter in source, make the surface temperature of polymer elements in treating processes be less than or equal to 100 ℃, for example be less than or equal to 50 ℃.
16., according to the method for any one in claim 6 to 15, wherein pending polymer elements is advanced with the speed of for example 5m/min to 100m/min in treatment facility.
17. according to the method for any one in claim 6 to 16, wherein by a plurality of multipotency X that produced by a plurality of ion sources +and X 2+ionic fluid, by ion implantation from the surface of pending polymer elements.
18., according to the method for any one in claim 6 to 17, wherein the type of the polymkeric substance of parts is selected from polycarbonate (PC), polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyamide (PA), polymethacrylate (PMMA), polyvinyl chloride (PVC) and/or polytetrafluoroethylene (PTFE).
19. according to the method for any one of the preceding claims, wherein said partitioning device comprises the storage tank that contains fluid product, is fixed on distribution member on described storage tank for example pump or valve, and the distributor head that is equipped with dispensing orifice is with for driving described distribution member.
20., according to the method for claim 1 to 18 any one, wherein said partitioning device comprises: a plurality of independent storage tanks, each storage tank contains a fluid dosage; Storage tank opening device, for example perforating needle; And the dosage-dispensing device for a fluid dosage is distributed by dispensing orifice from the storage tank of independent unlatching.
21. according to the method for any one of the preceding claims, wherein said fluid product is liquid or powder medicaments product, for the mode with nose or mouth, sprays and/or sucks.
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